Polymer member/inorganic base composite, production method therefor, and polymer member therefor

ABSTRACT

A composite of polymer member and inorganic substrate, a method of manufacturing the same, and a polymer member therefor are provided. A method for manufacturing a composite  210, 220  of polymer member and inorganic substrate includes: providing a composite  110, 120  of thermally modified polymer layer and inorganic substrate in which one or more thermally modified polymer layers  20, 21, 22  are adhered onto an inorganic substrate  10 , and bonding a polymer member  30, 31, 32  to the inorganic substrate via the one or more thermally modified polymer layers  20, 21, 22.

FIELD

The present invention relates to a composite of polymer member andinorganic substrate, a method of manufacturing the same, and a polymermember therefor.

BACKGROUND OF THE INVENTION

A polymer member, for example a polyolefin-based polymer such aspolypropylene, polyethylene, and cyclic olefin, has been widely used inmolded articles such as resin films, nonwoven fabrics, automotive parts,electronic equipment parts, and camera lenses because of their excellentlightness, mechanical strength, chemical resistance, and the like. Incontrast, inorganic materials such as metals, semiconductors, or oxidesthereof have different mechanical, thermal, optical, and chemicalproperties than the polymer member.

Accordingly, it has been studied to bond the polymer member to theinorganic substrate in order to utilize their different properties in apreferable manner.

In this regard, for example, in Patent Document 1, an inorganic materialand a polyolefin-based resin material are integrated without using anadhesive to provide a composite material useful for a microchip, aliquid crystal protective film for TV, and the like. Specifically, thisPatent Document 1 proposes a method for producing a composite materialcomprising an inorganic material and a polyolefin-based resin material,in which a thin film having a thickness of 1 to 50 nm consisting of anorganic material with a hydrophilic group is formed on a surface of aninorganic material, and the inorganic material on which the thin filmhas been formed and a polyolefin-based resin material are irradiatedwith ultraviolet rays having a wavelength of 100 to 200 nm,respectively, and then the polyolefin-based resin material is laminatedon the thin film of the inorganic material to integrate the inorganicmaterial and the polyolefin-based resin material.

RELATED ART Patent Literature

-   [Patent Document 1] JP-A-2013-103456

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

As described above, it may be preferable to bond a polymer member to aninorganic substrate without using an adhesive. Accordingly, in thepresent invention, there is provided a method useful for bonding apolymer member to an inorganic substrate without using an adhesive, aswell as a polymer member or the like used therefor.

Solution to the Problem

The present invention may include the following embodiments.

Embodiment 1

A method for manufacturing a composite of polymer member and inorganicsubstrate, comprising:

providing a composite of thermally modified polymer layer and inorganicsubstrate in which one or more thermally modified polymer layers areadhered onto an inorganic substrate, and

bonding a polymer member to the inorganic substrate via the one or morethermally modified polymer layers,

wherein the polymer member at least comprises inorganic particles and apolymer.

Embodiment 2

The method according to embodiment 1, wherein the polymer member furthercomprises a coupling agent.

Embodiment 3

The method according to embodiment 1 or 2, wherein the polymer member isin the form of a membrane or film.

Embodiment 4

The method according to any one of embodiments 1 to 3, wherein thebonding of the polymer member is performed by thermocompression bonding.

Embodiment 5

The method according to any one of embodiments 1 to 4, wherein the oneor more thermally modified polymer layers are formed of an olefinpolymer, and the polymer of the polymer member is an olefin polymer.

Embodiment 6

The method according to embodiment 5, wherein the olefin polymer is acyclic olefin polymer.

Embodiment 7

The method according to any one of embodiments 1 to 6, wherein theinorganic substrate is selected from a group consisting of metals andmetalloids, metal oxides and metalloid oxides, metal nitrides andmetalloid nitrides, metal carbides and metalloid carbides, carbonmaterials, and combinations thereof.

Embodiment 8

A composite of polymer member and inorganic substrate, comprising:

an inorganic substrate,

one or more thermally modified polymer layers adhered to the inorganicsubstrate, and

a polymer member adhered to the inorganic substrate via the one or morethermally modified polymer layers

wherein the polymer member at least comprises inorganic particles and apolymer.

Embodiment 9

The composite according to embodiment 8, wherein the polymer memberfurther comprises a coupling agent.

Embodiment 10

The composite according to embodiment 8 or 9, wherein the polymer memberis in the form of a membrane or film.

Embodiment 11

The composite according to any one of embodiments 8 to 10, wherein theone or more thermally modified polymer layers are formed of an olefinpolymer, and the polymer of the polymer member is an olefin polymer.

Embodiment 12

The composite according to embodiment 11, wherein the olefin polymer isa cyclic olefin polymer.

Embodiment 13

A polymer member at least comprising inorganic particles, a polymer, anda coupling agent.

Embodiment 14

The polymer member according to embodiment 13, which is in the form of amembrane or film.

Embodiment 15

The polymer member according to embodiment 13 or 14, wherein the averageprimary particle diameter of the inorganic particles is from 1 to 500nm.

Embodiment 16

A composite polymer member, comprising:

a polymer member at least comprising inorganic particles and a polymer;and

an additional polymer member at least comprising a polymer.

Embodiment 17

The composite polymer member according to embodiment 16, which is in theform of a membrane or film.

Embodiment 18

The composite polymer member according to embodiment 16 or 17, whereinthe inorganic particles have the average primary particle diameter of 1to 500 nm.

Embodiment 19

The composite polymer member according to any one of embodiments 16 to18, wherein at least one of the polymer member and the additionalpolymer member further comprises a coupling agent.

Embodiment 20

The composite polymer member according to embodiment 19, wherein thepolymer member is in the form of a film and further comprises a couplingagent, the additional polymer member is in the form of a film, furthercomprises inorganic particles, and does not comprise a coupling agent,and

the composite polymer member is in the form of a film.

Embodiment 21

The polymer member according to any one of embodiments 13 to 15 and thecomposite polymer member according to any one of embodiments 16 to 20,which are for optical use.

Advantageous Effects of Invention

According to the present disclosure, it is possible to provide a methodwhich is beneficial for bonding a polymer member to an inorganicsubstrate without using an adhesive, and a polymer member or the likeused therefor.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a schematic cross-sectional view of a composite of polymermember and inorganic substrate according to the present invention;

FIG. 1B is a schematic cross-sectional view of a composite of polymermember and inorganic substrate according to the present invention;

DETAILED DESCRIPTION OF THE EMBODIMENTS <<Method for Manufacturing aComposite of Polymer Member and Inorganic Substrate>>

The method for manufacturing a composite of polymer member and inorganicsubstrate according to the present invention comprises:

providing a composite of thermally modified polymer layer and inorganicsubstrate, in which one or more thermally modified polymer layers areadhered onto an inorganic substrate, and

bonding a polymer member to the inorganic substrate via the one or morethermally modified polymer layers.

Without wishing to be bound by theory, it is believed that according tothe method of the present invention for manufacturing a composite ofpolymer member and inorganic substrate, by bonding the polymer member tothe inorganic substrate via the one or more thermally modified polymerlayers, it is possible to improve the adhesion of the polymer member tothe inorganic substrate. With respect to the bonding of the polymermember and the inorganic substrate via the one or more thermallymodified polymer layers, the polymer member can be bonded directly tothe one or more thermally modified polymer layers, or to a thermallyunmodified polymer layer on the one or more thermally modified polymerlayers.

A method for manufacturing a composite of thermally modified polymerlayer and inorganic substrate in which one or more thermally modifiedpolymer layers are adhered onto an inorganic substrate may includeforming a first polymer layer on an inorganic substrate and then heatingthe first polymer layer to form a first thermally modified polymerlayer, in order to adhere the first thermally modified polymer layeronto the inorganic substrate.

Note that, in the composite of polymer member and inorganic substrateaccording to the present invention, the polymer member at leastcomprises inorganic particles and a polymer, and in particular at leastcomprises inorganic particles and a cyclic olefin polymer.

When the polymer member comprises inorganic particles, it is possible toadjust the physical properties, such as the refractive index, of thepolymer member.

In a preferred embodiment of the composite of polymer member andinorganic substrate according to the present disclosure, the polymermember at least comprises inorganic particles, a polymer, and a couplingagent, and in particular at least comprises inorganic particles, acyclic olefin polymer, and a silane coupling agent.

When the polymer member further comprises the coupling agent, theadhesion of the polymer member to the thermally modified polymer layercan be further improved. In particular, the adhesion of the polymermember to the thermally modified polymer layer can be further improved,when the adhesion of the polymer member to the thermally modifiedpolymer layer is reduced due to the inclusion of the inorganicparticles.

Without wishing to be bound by theory, it is believed that this isbecause the coupling agent, in particular the coupling agent adhered tothe surface of the inorganic particles, improves the dispersibility ofthe inorganic particles in the polymer member, and the remainingcoupling agent improves the adhesion of the polymer member to thethermally modified polymer layer.

<Inorganic Substrate>

The inorganic substrate used in the method of the present invention maybe any inorganic substrate, and may be selected from the groupconsisting of, for example, metals and metalloids, oxides of metals andmetalloids, nitrides of metals and metalloids, carbides of metals andmetalloids, carbon materials, and combinations thereof. Specifically,examples of the metal include aluminum, magnesium, titanium, nickel,chromium, iron, copper, gold, silver, tungsten, zirconium, yttrium,indium, iridium, and the like, and examples of the metalloid includesilicon, germanium, GaAs, InGaAs, InAlAs, LiTaOx, NbTaOx, ZnTe, GaSe,GaP, CdTe, diamond, diamond-like carbon, and the like. Therefore,examples of the metal oxide include oxides of these metals, and examplesof the metalloid oxide include oxides of these metalloids and the like.Examples of an oxide of silicon includes glass such as quartz glass andsoda glass, and examples of an oxide of aluminum include sapphire andthe like. The nitride may include aluminum nitride, silicon nitride, andthe like. The carbide include silicon carbide. Further, the carbonmaterial includes diamond and the like.

The surface of the inorganic substrate, in particular the metal or themetalloid, may be subjected to a treatment such as ozonation,ultraviolet treatment, or the like, in order to increase a functionalgroup, e.g., a hydroxyl group, which can be utilized for the bondingwith the first thermally modified polymer layer.

From the viewpoint of stably forming the thermally modified olefinpolymer layer on the inorganic substrate, an inorganic material having amelting point higher than the thermal modification temperature (thermaldenaturation temperature) of the thermally modified polymer layer can bepreferably used.

The inorganic substrate may be in any form, and may be, for example, inthe form of a film, a sheet, a plate, a tube, a rod, a disk, or thelike. In addition, the inorganic substrate may be of any size.

<Thermally Modified Polymer Layer>

A first polymer layer may be formed on an inorganic substrate, and thenthe first polymer layer may be heated to form a first thermally modifiedpolymer layer, in order to adhere the first thermally modified polymerlayer onto the inorganic substrate.

After the formation of the first thermally modified polymer layer, asecond polymer layer may be formed on the first thermally modifiedpolymer layer, and then the second polymer layer may be heated to form asecond thermally modified polymer layer, in order to adhere the secondthermally modified polymer layer onto the first thermally modifiedpolymer layer.

When the second thermally modified polymer layer is used, the degree ofthermal modification of the second thermally modified polymer layer maybe less than the degree of thermal modification of the first thermallymodified polymer layer, so that the first thermally modified polymerlayer provides good bonding to the inorganic substrate and the secondthermally modified polymer layer provides good bonding to the firstthermally modified polymer layer and the polymer member.

Further, in the method of the present invention, after forming thesecond thermally modified polymer layer, a third polymer layer may beformed on the second thermally modified polymer layer, and then thethird polymer layer may be heated to form a third thermally modifiedpolymer layer, in order to adhere the third thermally modified polymerlayer onto the second thermally modified polymer layer.

When the third thermally modified polymer layer is used, the degree ofthermal modification of the third thermally modified polymer layer maybe less than the degree of thermal modification of the second thermallymodified polymer layer, so that the second thermally modified polymerlayer provides good bonding to the first thermally modified polymerlayer and the third thermally modified polymer layer provides goodbonding to the second thermally modified polymer layer and the polymermember.

Further, additional thermally modified polymer layers such as a fourththermally modified polymer layer, a fifth thermally modified polymerlayer, or the like, can be used in the same manner.

The degree of thermal modification of these thermally modified polymerlayers can be adjusted by the temperature, time, ambient atmosphere, andthe like of the heating for thermal modification.

Specifically, for example, the degree of thermal modification of thefirst thermally modified polymer layer may be such that the firstthermally modified polymer layer adheres onto the inorganic substrate,i.e., such that the adhesion of the first thermally modified polymerlayer to the inorganic substrate is greater than the adhesion of thethermally unmodified first polymer layer to the inorganic substrate.

Similarly, the degree of thermal modification of the second thermallymodified polymer layer may be such that the second thermally modifiedpolymer layer adheres onto the first thermally modified polymer layer,i.e., such that the adhesion of the second thermally modified polymerlayer to the first thermally modified polymer layer is greater than theadhesion of the thermally unmodified second polymer layer to the firstthermally modified polymer layer.

Similarly, the degree of thermal modification of the third thermallymodified polymer layer may be such that the third thermally modifiedpolymer layer adheres to the second thermally modified polymer layer,i.e., such that the adhesion of the third thermally modified polymerlayer to the second thermally modified polymer layer is greater than theadhesion of the thermally unmodified third polymer layer to the secondthermally modified polymer layer.

The degree of thermal modification of these thermally modified polymerlayers can be adjusted, for example, by the heating temperature, theoxygen concentration in an atmosphere for heating, and the like, for thethermal modification of the thermally modified polymer layer. In otherwords, in order to increase the degree of thermal modification, theheating temperature can be increased and/or the oxygen concentration inthe atmosphere for heating can be increased. On the contrary, in orderto decrease the degree of thermal modification, the heating temperaturecan be decreased, and/or the oxygen concentration in the atmosphere forheating can be decreased.

The heating temperature for thermal modification of the thermallymodified polymer layer may be 50° C. or more, 100° C. or more, 140° C.or more, 160° C. or more, 180° C. or more, or 200° C. or more, and maybe 500° C. or less, 400° C. or less, 360° C. or less, 320° C. or less,or 280° C. or less. Further, this heating can be performed in anoxygen-containing atmosphere, in particular in air.

The degree of thermal modification of these thermally modified polymerlayers can be evaluated, for example, using the oxygen content of thethermally modified polymer constituting the thermally modified polymerlayer, specifically, the ratio of the number of oxygen atoms containedin the thermally modified polymer layer to the total number of oxygenatoms and carbon atoms contained in the thermally modified polymer layer(number of oxygen atoms/(number of oxygen atoms+number of carbonatoms)×100(%)). In this case, it is considered that the larger theratio, the larger the degree of thermal modification. A method forevaluating the content of oxygen atoms and carbon atoms of the thermallymodified polymer layer includes, for example, X-ray photoelectronspectroscopy (XPS). An XPS device for this purpose includes a K-Alpha(Thermo Fisher Scientific).

When such a ratio (number of oxygen atoms/(number of oxygen atoms+numberof carbon atoms)×100(%)) is 0.3% or more, 0.5% or more, 1.0% or more,2.0% or more, or 5.0% or more, and 50% or less, 30% or less, 20% orless, 10% or less, or 8% or less, it is particularly appropriate to usethis ratio as an index indicating the degree of thermal modification ofthe thermally modified polymer layer.

When evaluating the degree of thermal modification using the above ratio(number of oxygen atoms/(number of oxygen atoms+number of carbonatoms)×100(%)), the difference in this ratio between neighboringthermally modified polymer layers, such as the difference between theratio of the first thermally modified polymer layer and the ratio of thesecond thermally modified polymer layer, may be 0.1% or more, 0.2% ormore, 0.3% or more, 0.4% or more, 0.5% or more, 0.8% or more, 1.0% ormore, 2.0% or more, or 3.0% or more, and may be 10.0% or less, 7.0% orless, 5.0% or less, 3.0% or less, 2.0% or less, 1.0% or less, 0.5% orless, 0.3% or less or 0.1% or less.

In other words, for example, the ratio of the number of oxygen atomscontained in the second thermally modified polymer layer to the totalnumber of oxygen atoms and carbon atoms contained in the secondthermally modified polymer layer (i.e., the ratio of the number ofoxygen atoms/(the number of oxygen atoms+the number of carbonatoms)×100(%) for the second thermally modified polymer layer) may be0.1% or more and 10.0% or less smaller than the ratio of the number ofoxygen atoms contained in the first thermally modified polymer layer tothe total number of oxygen atoms and carbon atoms contained in the firstthermally modified polymer layer (i.e., the ratio of the number ofoxygen atoms/(the number of oxygen atoms+the number of carbonatoms)×100(%) for the first thermally modified polymer layer)

Further, the degree of thermal modification of these thermally modifiedpolymer layers can be evaluated, for example, by IR absorption spectrumof the thermally modified polymer constituting the thermally modifiedpolymer layer. An IR absorption analyzer for this purpose includesNicolet 6700 (Thermo Fisher SCIENTIFIC). Specifically, the degree ofthermal modification of the thermally modified polymer layer can beevaluated by the ratio of the intensity of the absorption peak of theC═O stretching vibration to the intensity of the absorption peak of theC—H stretching vibration (a ratio of the intensity of the absorptionpeak of C═O stretching vibration/intensity of the absorption peak of C—Hstretching vibration (−)). In this case, it is considered that thelarger the ratio, the larger the degree of thermal modification. Theintensity of the absorption peak can be determined by reading themaximum value of the absorbance value of the absorption peak.

When such a ratio (a ratio of intensity of absorption peak of C═Ostretching vibration/intensity of absorption peak of C—H stretchingvibration (−)) is 0.01 or more, 0.02 or more, 0.05 or more, 0.1 or more,0.15 or more, or 0.20 or more, and 20 or less, 10 or less, or 5 or less,it is particularly appropriate to use the ratio as an index indicatingthe degree of thermal modification of the thermally modified polymerlayer.

When the degree of thermal modification is evaluated using theabove-described ratio (a ratio of intensity of absorption peak of C═Ostretching vibration/intensity of absorption peak of C—H stretchingvibration (−)), the difference in this ratio between neighboringthermally modified polymer layers, such as the difference between theratio of the first thermally modified polymer layer and the ratio of thesecond thermally modified polymer layer, may be 0.1 or more, 0.2 ormore, 0.3 or more, 0.4 or more, 0.5 or more, 0.8 or more, 1.0 or more,2.0 or more, or 3.0 or more, and may be 10.0 or less, 7.0 or less, 5.0or less, 3.0 or less, 2.0 or less, 1.0 or less, 0.5 or less, 0.3 orless, or 0.1 or less.

In other words, for example, the ratio of the intensity of theabsorption peak of the C═O stretching vibration of the second thermallymodified polymer layer to the intensity of the absorption peak of theC—H stretching vibration of the second thermally modified polymer layer(i.e., the ratio of the intensity of the absorption peak of the C═Ostretching vibration/the intensity of the absorption peak of the C—Hstretching vibration (−) for the second thermally modified polymerlayer) may be 0.1 or more and 20.0 or less smaller than the ratio of theintensity of the absorption peak of the C═O stretching vibration of thefirst thermally modified polymer layer to the intensity of theabsorption peak of the C—H stretching vibration of the first thermallymodified polymer layer (i.e., the ratio of the intensity of theabsorption peak of the C═O stretching vibration/the intensity of theabsorption peak of the C—H stretching vibration (−) for the firstthermally modified polymer layer).

A method for the heating is not particularly limited. The method for theheating may include a method using a heating source such as an oven, ahot plate, infrared rays, a flame, a laser, or a flash lamp.

Note that the formation of the polymer layer such as the first polymerlayer can be performed by coating and/or thermocompression bonding.

When the formation of the polymer layer is carried out by coating, apolymer constituting the polymer layer may be dissolved in a solvent toform a solution, a coating may be carried out with this solution, andthen the coated solution may be dried to form a polymer layer. A coatingmethod in this case may include methods using a solution, such as a spincoating method, a roll coater method, a spray coating method, a diecoater method, an applicator method, an immersion coating method, abrush coating, a spatula coating, a roller coating, a curtain flowcoater method and the like.

When the polymer layer such as the first polymer layer is formed by amethod using a solution, the method may include a step of removing thesolvent by heating after the coating of the solution. In this case, asthe heating condition, it is possible to select temperature, heatingtime and atmospheric pressure condition which are sufficient to removethe solvent from the coating film.

Further, when the coating layer is formed by thermocompression bonding,it is possible to use a method of melting or welding a bulk solid, apowder, a film or the like while optionally applying pressure, such as ahot press method, a welding method, a powder coating method, or thelike.

Note that the thickness of the polymer layer such as the first polymerlayer may have any thickness, and may have a thickness which ensuresthat a thermally modified polymer layer to be obtained provides goodbonding between the inorganic substrate and the polymer member. Thethickness may be, for example, 1 nm or more, 5 nm or more, or 10 nm ormore, and may be 100 μm or less, 30 μm or less, or 10 μm or less, oreven 1000 nm or less, 500 nm or less, or 100 nm or less.

As described above, the thermally modified polymer layer is a layer viawhich the polymer member is bonded to the inorganic substrate.Therefore, this thermally modified polymer layer is preferably composedof the same type of polymer as the polymer constituting the polymermember, in order to promote the bonding between the thermally modifiedpolymer layer and the polymer member.

Thus, the polymer layer such as the first polymer layer may be formed ofan olefin polymer, for example, a cyclic olefin polymer.

Note that the olefin polymer means a polymer obtained by polymerizingmonomers containing an olefin as the main component; in other words, theolefin polymer means a polymer obtained by polymerizing monomerscontaining 50% by mass or more, 60% by mass or more, 70% by mass ormore, 80% by mass or more, 90% by mass or more, or 95% by mass or moreof a monomer portion derived from an olefin. Examples of the olefinpolymer include polyethylene, polypropylene, polybutene,polymethylpentene, copolymers of α-olefin and ethylene or propylene suchas propylene-ethylene copolymer and propylene-butene copolymer,styrene-butadiene-styrene block copolymer, styrene-hexadiene-styrenecopolymer, styrene-pentadiene-styrene copolymer,ethylene-propylene-diene copolymer (RPDM), cyclic olefin polymer, andthe like. However, the present invention is not limited to theseexamples. These olefin polymers may be used alone, or two or morethereof may be used in combination.

Among these olefin polymers, mention may be made, in particular, ofcyclic olefin polymers.

The cyclic olefin polymer is a polymer having a cyclic olefin portion inthe polymer main chain. Examples of such a cyclic olefin polymer includea ring-opening polymer of a cyclic olefin monomer, an addition polymerof a cyclic olefin monomer, a copolymer of a cyclic olefin monomer and alinear olefin, and the like. However, the present invention is notlimited to these examples.

The cyclic olefin monomer is a compound having a ring structure formedof carbon atoms and having a carbon-carbon double bond in the ringstructure. Examples of the cyclic olefin monomer include anorbornene-based monomer containing a norbornene ring, such as2-norbornene, norbornadiene and other bicyclic compounds,dicyclopentadiene, dihydrodicyclopentadiene and other tricycliccompounds, a tetracyclododecene, ethylidene-tetracyclododecene,phenyl-tetracyclododecene and other tetracyclic compounds,tricyclopentadiene and other five-membered ring compounds,tetracyclopentadiene and other seven-membered ring compounds; and amonocyclic cyclic olefin such as cyclobutene, cyclopentene, cyclooctene,cyclododecene, and 1,5-cyclooctadiene. However, the present invention isnot limited to these examples. The cyclic olefin monomer may havesubstituent(s) within a range in which the object of the presentinvention is not inhibited.

Cyclic olefin polymers are readily available commercially, for example,ZEONEX (trade name) Series and ZEONOR (trade name) Series, etc., fromZeon Corporation; SUMILITE (trade name) Series from Sumitomo BakeliteCo., LTD.; ARTON (trade name) Series from JSR Corporation; APEL Series,Mitsui Chemicals Inc.; TOPAS (trade name) from Ticona; Optolets Series,etc., from Hitachi Chemical Co., LTD.

When the polymer member is bonded to a thermally unmodified polymerlayer situated on one or more thermally modified polymer layers, thethermally unmodified polymer layer is preferably the same type ofpolymer as the thermally modified polymer layer such as the firstthermally modified polymer layer and the polymer member. For example,the thermally modified polymer layer such as the first thermallymodified polymer layer, the thermally unmodified polymer layer and thepolymer member may all be formed of an olefin polymer such as a cyclicolefin polymer. As for the specific materials and methods for theformation of the polymer member, reference may be made to the abovedescription regarding the thermally modified polymer layers such as thefirst thermally modified polymer layer.

<Polymer Member>

In the method of the present invention, the polymer member may be amember of any shape, and may be, for example, in the form of a membraneor film. In this case, the bonding of the polymer member may be carriedout by coating or thermocompression bonding, in particular bythermocompression bonding. The polymer member at least comprisesinorganic particles and a polymer, and particularly preferably at leastcomprises inorganic particles and a cyclic olefin polymer.

When the polymer member is in the form of a membrane or a film, thethickness thereof is preferably 1 cm or less, 5 mm or less, 2 mm orless, 1 mm or less, 500 μm or less, 200 μm or less, 100 μm or less, or50 μm or less, and 1 μm or more, 2 μm or more, 5 μm or more, 10 μm ormore, or 15 μm or more.

The polymer member preferably further comprises a coupling agent, inparticular a silane coupling agent.

Such a polymer member may be an optical member, in particular ananti-reflection film. The polymer member may consist of a plurality ofportions, and in particular, the polymer member may be a composite filmwhich is a laminate of a plurality of layers.

When the polymer member is a composite film which is a laminate of aplurality of layers, the number of layers of the laminate is preferably2 or more, and preferably 500 or less, 100 or less, 80 or less, 60 orless, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less.

The thermally modified polymer layer such as the first thermallymodified polymer layer and the polymer member are preferably the sametype of polymer. For example, the thermally modified polymer layer suchas the first thermally modified polymer layer and the polymer member maybe formed of an olefin polymer such as a cyclic olefin polymer. As forthe specific polymers and methods for the formation of the polymermember, reference may be made to the above description regarding thethermally modified polymer layers such as the first thermally modifiedpolymer layers.

(Inorganic Particle)

The inorganic particles in the present invention may include anyinorganic particles which can be dispersed in the polymer member, andexamples of such inorganic particles include particles of metal ormetalloid, particles of an oxide or fluoride of metal or metalloid, andparticles of compounds containing metal or metalloid.

As the metal or the metalloid, at least one selected from the groupconsisting of Si, Ge, Al, Mg, Ti, Ni, Cr, Fe, Cu, Au, Ag, W, Zr, Y, In,and Ir may be preferably used, and Si and Ge may be particularlypreferably used. Further, as the oxide and the fluoride of the metal orthe metalloid, at least one selected from the group consisting of MgO,Al₂O₃, Bi₂O₃, CaF₂, In₂O₃, In₂O₃.SnO₂, HfO₂, La₂O₃, MgF₂, Sb₂O₅,Sb₂O₅.SnO₂, SiO₂, SnO₂, TiO₂, Y₂O₃, ZnO and ZrO₂ may be preferably used,and MgO, Al₂O₃, SiO₂, TiO₂ may be particularly preferably used. Further,the compound containing the metal or the metalloid includes GaAs,InGaAs, InAlAs, LiTaOx, NbTaOx, ZnTe, GaSe, GaP, CdTe, diamond,diamond-like carbon, SiC, and the like.

When the inorganic particles are silicon particles, the inorganicparticles may be silicon particles obtained by a laser pyrolysis method,in particular, a laser pyrolysis method using a CO₂ laser.

The above inorganic particles, particularly the silicon particles, maycontain impurity elements such that the concentration of each impurityelement is 1000 ppm or less, 500 ppm or less, 300 ppm or less, 100 ppmor less, 50 ppm or less, 10 ppm or less, or 1 ppm or less, in order toobtain good optical properties. When the inorganic particles describedabove are silicon particles, examples of such impurities includeelements in Group 13 and Group 15.

Preferably, the average primary particle diameter of the inorganicparticles is 1 nm or more, or 3 nm or more, and 10000 nm or less, 5000nm or less, 2000 nm or less, 1000 nm or less, 500 nm or less, 200 nm orless, 100 nm or less, 50 nm or less, 30 nm or less, 20 nm or less, or 10nm or less.

In the present invention, the average primary particle diameter of theparticles may be obtained as the number average primary particlediameter, by taking images of the particles with a scanning electronmicroscope (SEM), a transmission electron microscope (TEM) or the like,by measuring the particle diameter directly based on the images, and byanalyzing a group of particles of 100 or more.

When the particle diameter is too large, scattering tends to occur,which may not be preferable. When the particle diameter of the particlesis too small, activation of the particle surface is facilitated due toan increase in the specific surface area of the particles, causing aremarkably high cohesiveness between the particles, and resulting inpoor handleability, which may not be preferable.

The content ratio of the inorganic particles may be, for example, suchthat the volume ratio of the polymer to the inorganic particles is 1:99to 99:1, 5:95 to 95:5, 10:90 to 85:15, 20:80 to 80:20, 30:70 to 75:25,or 40:60 to 70:30. When the content of the inorganic particle is toolow, the degree of adjustment of the refractive index and the like ofthe polymer member may be reduced, and when the content of the inorganicparticles is too high, the strength and the like as the polymer membermay not be maintained. When the polymer member is composed of aplurality of portions as described above, it is preferable that aportion of the polymer member to be bonded to a composite of thermallymodified polymer layer and inorganic substrate satisfies theabove-described volume ratio of the polymer and the inorganic particles.Thus, for example, when the polymer member is a composite film which isa laminate of a plurality of layers, it is preferable that a layer ofthe composite film to be bonded to a composite of thermally modifiedpolymer layer and inorganic substrate satisfies the above-describedvolume ratio of the polymer and the inorganic particles.

As the coupling agent in the present invention, any coupling agent whichcan be combined with the inorganic particles may be used. Specifically,as the coupling agent, a silane coupling agent, a titanate couplingagent, or an aluminate coupling agent may be used, and in particular, asilane coupling agent may be used. When an olefin polymer such as acyclic olefin polymer is used as a polymer of the polymer member, it ispossible to use a coupling agent with a functional group exhibiting goodmiscibility to these polymers, for example, a coupling agent with analkyl chain, a cyclohexyl group, or a benzene ring, and morespecifically, a coupling agent with an alkyl chain having 1 to 30, 1 to25, or 1 to 20 carbon atoms, a cyclohexyl group, or a benzene ring. Thecoupling agent and/or a hydrolytic condensate of the coupling agent maybe used alone or in combination of two or more.

Specifically, the coupling agent includes octadecyltriethoxysilane(OTS), octyltriethoxysilane, triethoxyphenylsilane,3-phenylpropyltriethoxysilane, cyclohexyltrimethoxysilane,octadecyltrimethoxysilane, octadecyltrichlorosilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane,γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropylmethyldimethoxysilane,γ-(2-aminoethyl)aminopropylmethyldiethoxysilane,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane,N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilanehydrochloride,N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilanehydrochloride, γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, vinyltriacetoxysilane,γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane,octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride,octadecyldimethyl[3-(triethoxysilyl)propyl]ammonium chloride,γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane,3-isocyanatopropyltrimethoxysilane, and3-isocyanatopropyltriethoxysilane.

The content ratio of the coupling agent may be, for example, such thatthe mass ratio of the inorganic particles to the coupling agent is 1:99to 99:1, 5:95 to 95:5, 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30,or 40:60 to 60:40. When the content of the coupling agent is too low,the adhesion between the polymer member and the thermally modifiedpolymer layer may be insufficient, and when the content of the couplingagent is too high, strength and the like as the polymer member may notbe maintained.

<<Composite of Polymer Member and Inorganic Substrate>>

In the composite of thermally modified polymer layer and inorganicsubstrate which can be used for the manufacturing of the composite ofpolymer member and inorganic substrate of the present invention, the oneor more thermally modified polymer layers are adhered to the inorganicsubstrate. In addition, in the composite of polymer member and inorganicsubstrate of the present invention, the polymer member is adhered to theinorganic substrate via the one or more thermally modified polymerlayers of the composite of thermally modified polymer layer andinorganic substrate of the present invention.

Specifically, as shown in FIG. 1A and FIG. 1B, in the composites ofpolymer member and inorganic substrate 210, 220 of the presentinvention, the polymer members 30, 31, 32 are bonded to the inorganicsubstrate 10 via the one or more thermally modified polymer layers 20,21, 22 of the composites of thermally modified polymer layer andinorganic substrate 110, 120.

According to the composite of polymer member and inorganic substrate ofthe present invention described above, it is possible to improve theadhesion of the polymer member to the inorganic substrate.

For details of each component of the composite of thermally modifiedpolymer layer and inorganic substrate of the present invention and thecomposite of polymer member and inorganic substrate of the presentinvention, reference may be made to the description relating to themethod of the present invention.

<<Composite Polymer Member>>

The polymer member according to the present disclosure may form acomposite polymer member together with an additional polymer member atleast comprising a polymer.

With respect to the additional polymer member, reference may be made tothe description relating to the polymer member, except that theadditional polymer member may not contain inorganic particles.

EXAMPLES Examples 1 to 9 and Comparative Example 1

In Examples 1 to 9, a laminate was formed which has, on a siliconsubstrate 10, first and second thermally modified polymer layers 21, 22and first and second anti-reflection layers 31, 32 as polymer members inthis order, as shown in FIG. 1B. For this laminate, the adhesion of theanti-reflection composite film composed of the first and secondanti-reflection layers to the silicon substrate was evaluated.

In Comparative Example 1, a laminate was formed which has, on a siliconsubstrate, first and second anti-reflection layers as polymer members inthis order. For this laminate, the adhesion of the anti-reflectioncomposite film composed of the first and second anti-reflection layersto the silicon substrate was evaluated.

Incidentally, in Examples 1 to 9 and Comparative Example 1, a cyclicolefin polymer (COP) (ZEONEX™ 480R; from Zeon Corporation; glasstransition temperature of 138° C.) was used as a material for both thethermally modified polymer layer and the polymer member.

Example 1 (1) Preparation of COP Solution A

A COP solution A was obtained by mixing and stirring 7% by mass of COPand 93% by mass of toluene at room temperature.

(2) Preparation of the Anti-Reflection Composite Film with the First andSecond Anti-Reflection Films

(a) Preparation of COP Solution B1 (Containing No Silicon Particles)

A COP solution B1 was obtained by mixing and stirring 35% by mass of COPand 65% by mass of toluene at room temperature

(b) Preparation of COP Solution B2 (Containing OTS-Treated SiliconParticles)

(b-1) Fabrication of Silicon Particles

Silicon particles were prepared by laser pyrolysis (LP) method usingcarbon dioxide laser, using monosilane gas as a raw material. Further,the metal impurity content of the obtained silicon particles wasmeasured using an inductively coupled plasma mass spectrometer (ICP-MS).As a result, the content of Fe was 15 ppb, the content of Cu was 18 ppb,the content of Ni was 10 ppb, the content of Cr was 21 ppb, the contentof Co was 13 ppb, the content of Na was 20 ppb, and the content of Cawas 10 ppb. The average primary particle diameter of the inorganicparticles was 100 nm.

(b-2) Surface Treatment of Silicon Particles

Silicon particles and octadecyltriethoxysilane (OTS) were placed in asealed container in an amount such that a ratio of silicon particles andOTS was 1:1 (mass ratio), and then, after mixing, heated to 120° C. andheld for 3 hours, to obtain OTS-treated silicon particles.

(b-3) Preparation of COP Solution B2

A COP solution was obtained by mixing and stirring 10% by mass of COPand 90% by mass of toluene at room temperature. To this COP solution,the OTS-treated silicon particles were added and mixed such that thevolume ratio of the COP and the silicon particles was 65:35. Further, byhomogenizing this mixture in a homogenizer for 15 minutes, a COPsolution B2 containing the OTS-treated silicon particles was prepared.

(c) Preparation of Anti-Reflection Composite Films

(c-1) Formation of Second Anti-Reflection Layer

The COP solution B1 obtained as described above was coated on a glasssubstrate using a doctor blade to obtain a coating film, and the solventin the coating film was removed by heating at 110° C., in order toobtain a second anti-reflection layer having a thickness of 25 μm on theglass plate.

(c-2) Formation of First Anti-Reflection Layer

The COP solution B2 obtained as described above was coated on the secondanti-reflection layer using a doctor blade to obtain a coating film, andthe solvent in the coating film was removed by heating at 110° C., inorder to form a first anti-reflection layer having a thickness of 20 μmon the second anti-reflection layer having a thickness of 25 μm.

(c-3) Peeling of Anti-Reflection Composite Film

The first and second anti-reflection layers obtained as described abovewere peeled off from the glass plate to obtain an anti-reflectioncomposite film (a composite polymer member) having the first and secondanti-reflection layers.

(3) Formation of First Thermally Modified Polymer Layer

A silicon substrate was used as an inorganic substrate, and a COPsolution A was spin-coated on the silicon substrate. The spin coatingwas performed by maintaining the rotation speed at 2000 rpm for 20seconds.

Thereafter, the silicon substrate coated with the COP solution A in thismanner was held on a hot plate heated to 120° C. and dried to obtain asilicon substrate having a first polymer layer. Thereafter, the firstpolymer layer was thermally modified (thermally denatured) by holdingthe substrate on a hot plate heated to 280° C. over a period of 1minutes, in order to form a first thermally modified polymer layerhaving a film thickness of 23 nm, which was adhered to the siliconsubstrate.

(4) Formation of Second Thermally Modified Polymer Layer

A COP solution A was spin-coated on the first thermally modified polymerlayer of the silicon substrate obtained as described above. The spincoating was performed by maintaining the rotation speed at 2000 rpm for20 seconds.

Thereafter, the silicon substrate coated with COP solution A in thismanner was held on a hot plate heated to 120° C. and dried to form asecond polymer layer on the first thermally modified polymer layer.Thereafter, the second polymer layer was thermally modified by holdingthe substrate on a hot plate heated to 200° C. for 2 minutes, in orderto form a second thermally modified polymer layer having a filmthickness of 23 nm, which was adhered onto the first thermally modifiedpolymer layer.

(5) Bonding of the Anti-Reflection Composite Film

The anti-reflection composite film obtained as described above wasadhered onto the second thermally modified polymer layer of the siliconsubstrate obtained as described above such that the firstanti-reflection layer was in contact with the second thermally modifiedpolymer layer, and thermocompression bonding was performed at 115° C.and 0.2 MPa pressure for 60 minutes to adhere the anti-reflectioncomposite film onto the second thermally modified polymer layer. Theobtained evaluation laminate had, on the silicon substrate, the firstthermally modified polymer layer, the second thermally modified polymerlayer, the first anti-reflection layer, and the second anti-reflectionlayer in this order.

(Cross-Cut Test)

The evaluation laminate obtained as described above was subjected to across-cut test.

Specifically, on the anti-reflection composite film formed on thesilicon substrate, cuts were made at 1 mm intervals to reach the siliconsubstrate using a utility knife. After six cuts were made, six more cutswere made orthogonal to these cuts, in order to form grid-like cuts.

Thereafter, Scotch-Mending Tape (manufactured by 3M Company; 810, 24-mmwide) was applied to the surfaces of the polymer member, and afterfinger-rubbing the tape from above to adhere it, the tape was peeledoff. The area where the tape was stuck and peeled off in this way wasobserved by a stereomicroscope.

The evaluation results were classified as follows.

A: The edges of the cuts were perfectly smooth and no peeling wasobserved in any cells of the grid.

B: Although the polymer member was partially peeled off, less than 35%of the cross-cut section was affected.

C: Large part of the polymer member was peeled off; 35% or more of thecross-cut section was affected.

D: A cross-cut test was not performed because of poor adhesion of thepolymer member to the substrate.

In the anti-reflection composite film of Example 1, the edges of the cutwere completely smooth, and no peeling was observed in any cells of thegrid (Rating A). The preparation conditions and evaluation results ofthe evaluation laminate according to Example 1 having the first andsecond thermally modified polymer layers and the first and secondanti-reflection layers on the silicon substrate are shown in Table 1below.

Examples 2 to 8

Evaluation laminates of Examples 2 to 8 having first and secondthermally modified polymer layers and first and second anti-reflectionlayers on a silicon substrate were obtained in the same manner as inExample 1 except that a spray method was used as the method of formingthe second anti-reflection layer (Example 2) and the volume ratio of theCOP and the silicon particles was changed in the COP solution forpreparing COP solution B2 (Examples 3 to 8). The evaluation laminates ofExamples 2 to 8 were evaluated in the same manner as in Example 1. Thepreparation conditions and evaluation results of the evaluationlaminates according to Examples 2 to 8 are shown in Table 1 below.

Example 9

An evaluation laminate having first and second thermally modifiedpolymer layers and first and second anti-reflection layers on a siliconsubstrate was obtained in the same manner as in Example 1, except thatthe COP solution B2′ (containing non-OTS-treated silicon particles) wasobtained without performing surface treatment of the silicon particlesusing OTS in the manufacturing process of the COP solution B2, and thatthis COP solution B2′ was used instead of the COP solution B2. Theevaluation laminate according to Example 9 was evaluated in the samemanner as in Example 1. The preparation conditions and evaluationresults of the evaluation laminate according to Example 9 are shown inTable 1 below.

Comparative Example 1

An evaluation laminate having first and second anti-reflection layers ona silicon substrate was obtained in the same manner as in Example 9except that the first and second thermally modified polymer layers werenot formed. This evaluation laminate according to Comparative Example 1was evaluated in the same manner as in Example 1. The preparationconditions and evaluation results of the evaluation laminate accordingto Comparative Example 1 are shown in Table 1 below.

Example 10

An evaluation laminate having first and second thermally modifiedpolymer layers and first to fourth anti-reflection layers on a siliconsubstrate was obtained in the same manner as in Example 1, except asfollows:

(i) A coating film was obtained by applying a COP solution B1 on a glassplate using a doctor blade, and a solvent in the coating film wasremoved by heating at 110° C. to obtain a fourth anti-reflection layerhaving a thickness of 25 μm on the glass plate;

(ii) After (i) above, a coating film was obtained by applying the COPsolution B2 on the fourth anti-reflection layer using a doctor blade,and a solvent in the coating film was removed by heating at 110° C. toobtain a third anti-reflection layer having a thickness of 20 μm on thefourth anti-reflection layer;

(iii) Further, after (ii) above, a coating film was obtained by applyingthe COP solution B1 on the third anti-reflection layer using a doctorblade, and a solvent in the coating film was removed by heating at 110°C. to obtain a second anti-reflection layer having a thickness of 25 μmon the third anti-reflection layer;

(iv) Further, after (iii) above, a coating film was obtained by applyingCOP solution B2 on the second anti-reflection layer using a doctorblade, and a solvent in the coating film was removed by heating at 110°C. to obtain a first anti-reflection layer having a thickness of 20 μmon the second anti-reflection layer.

This evaluation laminate according to Example 10 was evaluated in thesame manner as in Example 1. The preparation conditions and evaluationresults of the evaluation laminate according to Example 10 are shown inTable 2 below.

Example 11

An evaluation laminate having first and second thermally modifiedpolymer layers and first to third anti-reflection layers on a siliconsubstrate was obtained in the same manner as in Example 1, except asfollows:

(i) A coating film was obtained by coating a COP solution B1 on a glassplate using a doctor blade, and a solvent in the coating film wasremoved by heating at 110° C. to obtain a third anti-reflection layerhaving a thickness of 25 μm on the glass plate;

(ii) After (i) above, a coating film was obtained by applying the COPsolution B2′ used in Example 9, i.e., the COP solution containingsilicon particles not subjected to a surface treatment with OTS, on thethird anti-reflection layer using a doctor blade, and a solvent in thecoating film was removed by heating at 110° C. to obtain a secondanti-reflection layer having a thickness of 15 μm on the thirdanti-reflection layer;

(iii) Further, after (ii) above, a coating film was obtained by applyingCOP solution B2 on the second anti-reflection layer using a doctorblade, and a solvent in the coating film was removed by heating at 110°C. to obtain a first anti-reflection layer having a thickness of 5 μm onthe second anti-reflection layer.

This evaluation laminate according to Example 11 was evaluated in thesame manner as in Example 1. The preparation conditions and evaluationresults of the evaluation laminate according to Example 11 are shown inTable 2 below.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Inorganicsubstrate Si Si Si Si Si First thermally Polymer C0P C0P C0P C0P C0Pmodified Thermal 280° C. 280° C. 280° C. 280° C. 280° C. polymer layermodification temp. Second thermally Polymer C0P C0P C0P C0P C0P modifiedThermal 200° C. 200° C. 200° C. 200° C. 200° C. polymer layermodification temp. First Polymer C0P C0P C0P C0P C0P anti-reflectionFiller Si particles Si particles Si particles Si particles Si particleslayer Filler content 35 vol % 35 vol % 30 vol % 25 vol % 20 vol %Coupling agent 0TS 0TS 0TS 0TS 0TS Preparation Blade Blade Blade BladeBlade method coating coating coating coating coating Thickness 20 μm 20μm 20 μm 20 μm 20 μm Second Polymer C0P C0P C0P C0P C0P anti-reflectionFiller — — — — — layer Filler content — — — — — Coupling agent — — — — —Preparation Blade Spraying Blade Blade Blade method coating coatingcoating coating Thickness 25 μm 25 μm 25 μm 25 μm 25 μm Bonding methodfor Thermo- Thermo- Thermo- Thermo- Thermo- anti-reflection compositefilm compression compression compression compression compression bondingbonding bonding bonding bonding Evaluation result A A A A A Comp.Example 6 Example 7 Example 8 Example 9 Example 1 Inorganic substrate SiSi Si Si Si First thermally Polymer C0P C0P C0P C0P — modified Thermal280° C. 280° C. 280° C. 280° C. — polymer layer modification temp.Second thermally Polymer C0P C0P C0P C0P — modified Thermal 200° C. 200°C. 200° C. 200° C. — polymer layer modification temp. First Polymer C0PC0P C0P C0P C0P anti-reflection Filler Si particles Si particles Siparticles Si particles Si particles layer Filler content 15 vol % 10 vol% 5 vol % 35 vol % 35 vol % Coupling agent 0TS 0TS 0TS — — PreparationBlade Blade Blade Blade Blade method coating coating coating coatingcoating Thickness 20 μm 20 μm 20 μm 20 μm 20 μm Second Polymer C0P C0PC0P C0P C0P anti-reflection Filler — — — — — layer Filler content — — —— — Coupling agent — — — — — Preparation Blade Blade Blade Blade Blademethod coating coating coating coating coating Thickness 25 μm 25 μm 25μm 25 μm 25 μm Bonding method for Thermo- Thermo- Thermo- Thermo Thermo-anti-reflection composite film compression compression compressioncompression compression bonding bonding bonding bonding bondingEvaluation result A A A C D

TABLE 2 Example 10 Example 11 Inorganic substrate Si Si First thermallyPolymer COP COP modified polymer Thermal 280° C. 280° C. layermodification temp. Second thermally Polymer COP COP modified polymerThermal 200° C. 200° C. layer modification temp. First anti- Polymer COPCOP reflection layer Filler Si particles Si particles Filler content 35vol % 35 vol % Coupling agent OTS OTS Preparation method Blade coatingBlade coating Thickness 20 μm 5 μm Second anti- Polymer COP COPreflection layer Filler — Si particles Filler content — 35 vol %Coupling agent — — Preparation method Blade coating Blade coatingThickness 25 μm 15 μm Third anti- Polymer COP COP reflection layerFiller Si particles — Filler content 5 vol % — Coupling agent OTS —Preparation method Blade coating Blade coating Thickness 20 μm 25 μmFourth anti- Polymer COP — reflection layer Filler — — Filler content —— Coupling agent — — Preparation method Blade coating — Thickness 25 μm— Bonding method for anti-reflection (※) (※) composite film Evaluationresult A A (※) Thermocompression bonding

From the comparison between Examples 1 to 11 and Comparative Example 1,it is understood that by bonding an anti-reflection film (polymermember) to an inorganic substrate via a thermally modified polymerlayer, adhesion of the anti-reflection film to the inorganic substrateis improved.

Further, as can be seen in Table 1 and Table 2, it is understood thatwhen an anti-reflection film (polymer member) contains a coupling agent,adhesion between the thermally modified polymer layer and theanti-reflection film is further improved even when the anti-reflectionlayer contains inorganic particles.

Reference Examples 1 to 14 and Reference Comparative Examples 1 and 2

In the following Reference Examples and Reference Comparative Examples,the formation of thermally modified polymer layers and the adhesion of apolymer member to a thermally modified polymer layer are evaluated.

Polymers used for the formation of thermally modified polymer layers andpolymer members in the following reference examples are as follows:

COP1: Cyclic olefin polymer (ARTON™ (JSR Corporation))

COP2: Cyclic olefin polymer (Zeon Corporation, ZEONEX™ 480R, glasstransition temperature 138° C.)

Reference Examples 1 to 14 and Reference Comparative Examples 1 and 2

As described below, in Reference Examples 1 to 14, COP1 was used as amaterial for both thermally modified polymer layers and polymer members.In addition, in Reference Comparative Examples 1 and 2, thermallymodified polymer layers were not used, and COP1 was used as a materialof a polymer member.

Reference Example 1 (Preparation of Solution for Thermally ModifiedPolymer Layer)

A solution for thermally modified polymer layer was obtained by mixingand stirring 7% by mass of COP1 and 93% by mass of chloroform at roomtemperature.

(Formation of First Thermally Modified Polymer Layer)

A silicon substrate was used as inorganic substrate, and the solutionfor thermally modified polymer layer was spin-coated on the siliconsubstrate. The spin coating was performed by maintaining the rotationspeed at 2000 rpm for 20 seconds.

Thereafter, the silicon substrate coated with the solution for thermallymodified polymer layer in this manner was held on a hot plate heated to120° C. to dry the solution for thermally modified polymer layer, inorder to obtain a silicon substrate with a first polymer layer, and thenthe first polymer layer was thermally modified (thermally denatured) byholding the substrate on a hot plate heated to 280° C. for 1 minutes toobtain a silicon substrate with a first thermally modified polymer layerhaving a film thickness of 23 nm.

(Formation of Second Thermally Modified Polymer Layer)

The solution for thermally modified polymer layer was spin-coated on thefirst thermally modified polymer layer of the silicon substrate obtainedas described above. The spin coating was performed by maintaining therotation speed at 2000 rpm for 20 seconds.

Thereafter, the silicon substrate coated with the solution for thermallymodified polymer layer in this manner was held on a hot plate heated to120° C. to dry the solution for thermally modified polymer layer, inorder to form a second polymer layer on the first thermally modifiedpolymer layer. Then, the second polymer layer was thermally modified byholding the substrate on a hot plate heated to 200° C. for 2 minutes toobtain a second thermally modified polymer layer having a film thicknessof 23 nm, which was adhered onto the first thermally modified polymerlayer. A composite of thermally modified polymer layer and inorganicsubstrate thus obtained was used as the composite of thermally modifiedpolymer layer and inorganic substrate according to Reference Example 1.

(Preparation of Solution for Polymer Member)

A solution for polymer member was obtained by mixing and stirring 7% bymass of COP1 and 93% by mass of chloroform at room temperature.

(Bonding of Polymer Member)

The solution for polymer member was spin-coated on the second thermallymodified polymer layer obtained as described above. The spin coating wasperformed by maintaining the rotation speed at 2000 rpm for 20 seconds.

Thereafter, the silicon substrate coated with the solution for polymermember in this manner was held on a hot plate heated to 140° C. for 10minutes to dry the solution for polymer member, in order to bond apolymer member having a film thickness of 23 nm onto the secondthermally modified polymer layer. A composite of polymer member andinorganic substrate thus obtained was used as the composite of polymermember and inorganic substrate according to Reference Example 1.

(Cross-Cut Test)

On the laminate of the first and second thermally modified polymerlayers and the polymer member formed on the silicon substrate, cutsreaching the silicon substrate were made at 1 mm intervals by using autility knife. After six cuts were made, six more cuts were madeorthogonal to these cuts to form grid-like cuts.

Thereafter, Scotch-Mending Tape (3M Company; 810, 24-mm wide) wasapplied to the surfaces of the polymer member, and after finger-rubbingthe tape from above to adhere it, the tape was peeled off. The areawhere the tape was stuck and peeled off in this way was observed by astereomicroscope.

The evaluation results were classified as follows.

A: The edges of the cuts were perfectly smooth and no peeling wasobserved in any cells of the grids.

B: Although the polymer member was partially peeled off, less than 35%of the cross-cut section was affected.

C: Large part of the polymer member was peeled off, and 35% or more ofthe cross-cut section was affected.

In the composite of polymer member and inorganic substrate of ReferenceExample 1, the edges of the cuts were completely smooth, and no peelingwas observed in any cells of the grids (Rating A). The preparationconditions and evaluation results for this composite material are shownin Table R1 below.

Reference Examples 2 to 8

Composites of polymer member and inorganic substrate according toReference Examples 2 to 8 was prepared in the same manner as inReference Example 1, except that the concentration of the polymer in thesolution for thermally modified polymer layer was changed (ReferenceExamples 2 and 3), the spin coating condition of the solution forthermally modified polymer layer was changed (Reference Example 4), orthe temperature of thermal modification of the first thermally modifiedpolymer was changed (Reference Examples 5 to 8), as in Tables R1 and R2.The composites thus prepared were evaluated in the same manner as inReference Example 1. The preparation conditions and evaluation resultsof these composite materials are shown in Tables R1 and R2 below.

Reference Example 3A (Formation of First and Second Thermally ModifiedPolymer Layers)

A first thermally modified polymer layer and a second thermally modifiedpolymer were formed on a silicon substrate in the same manner as inReference Example 1, except that the temperature of thermal modificationfor the first thermally modified polymer was 300° C., and thetemperature of thermal modification for the second thermally modifiedpolymer was 280° C. and the treatment was performed for 1 minute.

(Formation of Third Thermally Modified Polymer Layer)

The solution for thermally modified polymer layer was spin-coated on thesecond thermally modified polymer layer obtained as described above. Thespin coating was performed by maintaining the rotation speed at 2000 rpmfor 20 seconds.

Thereafter, the silicon substrate coated with the solution for thermallymodified polymer layer in this manner was held on a hot plate heated to120° C. to dry the solution for thermally modified polymer layer, inorder to form a third polymer layer on the second thermally modifiedpolymer layer. Then, the third polymer layer was thermally modified byholding the substrate on a hot plate heated to 200° C. for 2 minutes toobtain a third thermally modified polymer layer having a film thicknessof 23 nm, which was adhered onto the second thermally modified polymerlayer. A composite of thermally modified polymer layer and inorganicsubstrate thus obtained was used as the composite of thermally modifiedpolymer layer and inorganic substrate of Reference Example 3A

(Bonding of Polymer Member)

Thereafter, the composite of polymer member and inorganic substrateaccording to Reference Example 3A was prepared by performing bonding ofthe polymer member in the same manner as in Reference Example 1.

(Cross-Cut Test)

The composite of polymer member and inorganic substrate according toReference Example 3A was evaluated in the same manner as in ReferenceExample 1.

The preparation conditions and evaluation results of this compositematerial are shown in Table R1 below.

Reference Comparative Example 1

The composite of polymer member and inorganic substrate according toReference Comparative Example 1 was prepared in the same manner as inReference Example 1, except that first and second thermally modifiedpolymer layers were not formed on a silicon substrate which was used asan inorganic substrate, and that COP1 was spin-coated directly on thesilicon substrate. The obtained composite was evaluated in the samemanner as in Reference Example 1. The preparation conditions andevaluation results of this composite material are shown in Tables R1 andR2 below.

Reference Example 9

The composite of polymer member and inorganic substrate according toReference Example 9 was prepared and evaluated in the same manner as inReference Example 1, except that instead of spin-coating the cyclicolefin polymer during bonding of the polymer member, a film of COP1(with a thickness of 100 μm) was placed on the second thermally modifiedpolymer layer and held at 50 MPa pressure and 140° C. for 2 hours forthe thermocompression-bonding of the film and the second thermallymodified polymer layer. The preparation conditions and evaluationresults of this composite material are shown in Table R3 below.

Reference Comparative Example 2

The composite polymer member and inorganic substrate according toReference Comparative Example 2 was prepared in the same manner as inReference Example 9, except that first and second thermally modifiedpolymer layer were not formed on a silicon substrate which was used asan inorganic substrate, and a film of COP1 (thickness: 100 μm) wasbonded directly onto the silicon substrate by thermocompression-bonding.The obtained composite was evaluated in the same manner as in ReferenceExample 1. The preparation conditions and evaluation results of thiscomposite material are shown in Table R3 below.

Reference Examples 10 to 14

Composites of polymer member and inorganic substrate according toReference Examples 10 to 14 were prepared in the same manner as inReference Examples 5, 6, 1, 7 and 8, respectively, except that after thefirst thermally modified polymer layer was formed on the siliconsubstrate which was used as an inorganic substrate, a solution forpolymer member was spin-coated directly on the first thermally modifiedpolymer layer without forming a second thermally modified polymer layer.The obtained composites were evaluated in the same manner as inReference Example 1. The preparation conditions and evaluation resultsfor these composite materials are shown in Table R4 below.

Reference Examples 15 to 20 and Reference Comparative Example 3

As described below, in Reference Examples 15 to 20, COP2 was used as amaterial for both the thermally modified polymer layer and the film ofthe polymer member. In addition, in Reference Comparative Example 3, thethermally modified polymer layer was not used, and COP2 was used as amaterial of the film of the polymer member.

Reference Example 15

The composite of polymer member and inorganic substrate according toReference Example 15 was prepared in the same manner as in ReferenceExample 1, except that in the preparation of both the solution forthermally modified polymer layer and the solution for polymer member, asolution for thermally modified polymer layer was obtained by mixing andstirring 10% by mass of COP2 and 90% by mass of toluene at roomtemperature. The obtained composite was evaluated in the same manner asin Reference Example 1. The conditions and evaluation results of thiscomposite material are shown in Table R5 below.

Reference Example 16

The composite of polymer member and inorganic substrate according toReference Example 16 was prepared in the same manner as in ReferenceExample 15, except that the concentration of polymer in the solution forforming thermally modified polymer layer was changed from 10% by mass to1% by mass. The obtained composite was evaluated in the same manner asin Reference Example 1. The preparation conditions and evaluationresults of this composite are shown in Table R5 below.

Reference Comparative Example 3

The composite of polymer member and inorganic substrate according toReference Comparative Example 3 was prepared in the same manner as inReference Example 15, except that first and second thermally modifiedpolymer layers were not formed on the silicon substrate which was usedas an inorganic substrate, and that COP2 was spin-coated directly on thesilicon substrate. The obtained composite was evaluated in the samemanner as in Reference Example 1. The preparation conditions andevaluation results for this composite material are shown in Table R5below.

Reference Examples 17 to 20

Composites of polymer member and inorganic substrate according toReference Examples 17 to 20 were prepared in the same manner as inReference Example 15, except that the temperature of thermalmodification for the first thermally modified polymer was changed as inTable R6. The obtained composites were evaluated in the same manner asin Reference Example 1. The preparation conditions and evaluationresults for these composite materials are shown in Table R6 below.

Reference Example 21 and Reference Comparative Example 4

As described below, in Reference Example 21, a polyethylene (PE) film(thickness: 30 μm) was used as a material for both the thermallymodified polymer layer and the polymer member. In addition, in ReferenceComparative Example 4, the thermally modified polymer layer was notused, and a polyethylene film (thickness: 30 μm) was used as a materialof the polymer member.

Reference Example 21 (Formation of First Thermally Modified PolymerLayer)

A silicone substrate as inorganic substrate having a polyethylene film(30 μm thickness) thereon was heated to 120° C. and held for 1 minute toobtain a silicon substrate with a polyethylene film, and then thepolyethylene film was thermally modified by holding the substrate on ahot plate heated to 280° C. for 1 minute, in order to obtain a siliconsubstrate with a first thermally modified polymer layer.

(Formation of Second Thermally Modified Polymer Layer)

A polyethylene film (thickness: 30 μm) was placed on the first thermallymodified polymer layer of the silicon substrate obtained as describedabove, and the substrate was heated to 120° C. and held for 1 minute toadhere the polyethylene film onto the first thermally modified polymerlayer. Then, the polyethylene film was thermally modified by holding thesubstrate on a hot plate heated to 200° C. for 2 minutes, in order toobtain a second thermally modified polymer layer, which was adhered ontothe first thermally modified polymer layer. A composite of thermallymodified polymer layer and inorganic substrate thus obtained was used asthe composite of thermally modified polymer layer and inorganicsubstrate according to Reference Example 21.

(Bonding of Polymer Member)

A polyethylene film (thickness: 30 μm) was placed on the secondthermally modified polymer layer obtained as described above, and thesubstrate was heated to 120° C. and held for 1 minute, and furtherheated to 140° C. and held for 10 minutes, to bond the polyethylene filmas polymer member onto the first thermally modified polymer layer. Acomposite of polymer member and inorganic substrate thus obtained wasused as the composite of polymer member and inorganic substrateaccording to Reference Example 21, and evaluated in the same manner asin Reference Example 1. The preparation conditions and evaluationresults for this composite material are shown in Table R7 below.

Reference Comparative Example 4

The composite of polymer member and inorganic substrate according toReference Comparative Example 4 was prepared in the same manner as inReference Example 21, except that first and second thermally modifiedpolymer layer were not formed on a silicon substrate which was used asan inorganic substrate, and a polyethylene film as polymer member wasbonded directly onto the silicon substrate. The obtained composite wasevaluated in the same manner as in Reference Example 1. The preparationconditions and evaluation results for this composite material are shownin Table R7 below.

Reference Examples 22 to 27

As described below, in Reference Examples 22 to 27, different polymerswere used for the material of thermally modified polymer layer and forthe material of polymer member.

Reference Examples 22 and 23 (Formation of First and Second ThermallyModified Polymer Layer)

A silicon substrate was used as an inorganic substrate, and, as inReference Example 1, COP1 was used to form first and second thermallymodified polymer layers on the silicon substrate.

(Bonding of Polymer Member)

In Reference Example 22, the solution for polymer member of COP2obtained as described in Reference Example 15 was spin-coated on thesecond thermally modified polymer layer obtained as described above, anddried to form a composite of polymer member and inorganic substrateaccording to Reference Example 22. The obtained composite was evaluatedin the same manner as in Reference Example 1. The preparation conditionsand evaluation results for this composite material are shown in Table R8below.

In Reference Example 23, a polyethylene film (thickness: 30 μm) wasbonded as in Reference Example 21 on the second thermally modifiedpolymer layer obtained as described above to form a composite of polymermember and inorganic substrate according to Reference Example 23. Theobtained composite was evaluated in the same manner as in ReferenceExample 1. The preparation conditions and evaluation results of thiscomposite material are shown in Table R8 below.

Reference Examples 24 and 25 (Formation of First and Second ThermallyModified Polymer Layer)

A silicon substrate was used as an inorganic substrate, and as inReference Example 15, COP2 was used to form first and second thermallymodified polymer layers on the silicon substrate.

(Bonding of Polymer Member)

In Reference Example 24, the solution for polymer member of COP1obtained as described in Reference Example 1 was spin-coated on thesecond thermally modified polymer layer obtained as described above, anddried to form a composite of polymer member and inorganic substrateaccording to Reference Example 24. The obtained composite was evaluatedin the same manner as in Reference Example 1. The preparation conditionsand evaluation results of this composite material are shown in Table R8below.

In Reference Example 25, a polyethylene film (thickness: 30 μm) wasbonded as in Reference Example 21 on the second thermally modifiedpolymer layer obtained as described above to form a composite of polymermember and inorganic substrate according to Reference Example 25. Theobtained composite was evaluated in the same manner as in ReferenceExample 1. The preparation conditions and evaluation results for thiscomposite material are shown in Table R8 below.

Reference Examples 26 and 27 (Formation of First and Second ThermallyModified Polymer Layer)

A silicon substrate was used as an inorganic substrate, and as inReference Example 21, a polyethylene film (thickness: 30 μm) was used toform first and second thermally modified polymer layer on the siliconsubstrate.

(Bonding of Polymer Member)

In Reference Example 26, the solution for polymer member of COP1obtained as described in Reference Example 1 was spin-coated on thesecond thermally modified polymer layer obtained as described above, anddried to form a composite of polymer member and inorganic substrateaccording to Reference Example 26. The obtained composite was evaluatedin the same manner as in Reference Example 1. The preparation conditionsand evaluation results of this composite material are shown in Table R8below.

In Reference Example 27, the solution for polymer member of COP2obtained as described in Reference Example 15 was spin-coated on thesecond thermally modified polymer layer obtained as described above, anddried to form a composite of polymer member and inorganic substrate ofReference Example 26. The obtained composite was evaluated in the samemanner as in Reference Example 1. The preparation conditions andevaluation results of this composite material are shown in Table R8below.

Reference Examples 28 to 30 and Reference Comparative Examples 5 to 7Reference Examples 28 to 30

Composites of polymer member and inorganic substrate according toReference Examples 28 to 30 were prepared in the same manner as inReference Example 15, except that a silicon substrate with an SiN layerformed on the surface thereof (Reference Example 28), a copper plate(Reference Example 29), and an aluminum plate (Reference Example 30)were used as an inorganic substrate, respectively, instead of a siliconsubstrate. The obtained composites were evaluated in the same manner asin Reference Example 1. The preparation conditions and evaluationresults of these composite materials are shown in Table R9 below.

Reference Comparative Examples 5 to 7

Composites of polymer member and inorganic substrate according toReference Comparative Examples 5 to 7 were prepared in the same manneras in Reference Examples 28 to 30, respectively, except that thethermally modified polymer layer was not used. The obtained compositeswere evaluated in the same manner as in Reference Example 1. Thepreparation conditions and evaluation results of these compositematerials are shown in the following table.

Reference Comparative Examples 8 to 13

As described below, in Reference Comparative Examples 8 to 13, a siliconsubstrate as inorganic substrate was treated with a silane couplingagent, and a polymer member was bonded to this treated surface.

Reference Comparative Examples 8 and 9

An OTS-treated silicon substrate was obtained by treating a siliconsubstrate as an inorganic substrate with ultraviolet and ozone (UV/O₃treatment), and then by holding the substrate for 3 hours in a saturatedvapor pressure atmosphere at 150° C. of octadecyltriethoxysilane (OTS)as a silane coupling agent.

In Reference Comparative Example 8, without forming a thermally modifiedpolymer layer on the surface of the OTS-treated silicon substrate thusobtained, a polymer member was bonded by spin-coating in the same manneras in Reference Example 15 to form a composite of polymer member andinorganic substrate according to Reference Comparative Example 8. Theobtained composite was evaluated in the same manner as in ReferenceExample 1. The preparation conditions and the evaluation results forthis composite material are shown in Table R10 below.

In Reference Comparative Example 9, without forming a thermally modifiedpolymer layer on the surface of the OTS-treated silicon substrate thusobtained, a polymer member was bonded by thermocompression-bonding inthe same manner as in Reference Example 21 to form a composite ofpolymer member and inorganic substrate according to ReferenceComparative Example 9. The obtained composite was evaluated in the samemanner as in Reference Example 1. The preparation conditions andevaluation results of this composite material are shown in Table R10below.

Reference Comparative Examples 10 and 11

Composites of polymer member and inorganic substrate according toReference Comparative Examples 10 to 11 were prepared in the same manneras in Reference Comparative Examples 8 and 9, respectively, except that3-phenylpropyltriethoxysilane (PTS) was used as a silane coupling agentinstead of octadecyltriethoxysilane (OTS). The obtained composites wereevaluated in the same manner as in Reference Example 1. The preparationconditions and evaluation results of these composite material are shownin Table R10 below.

Reference Comparative Examples 12 and 13

Composites of polymer member and inorganic substrate according toReference Comparative Examples 12 to 13 were prepared in the same manneras in Reference Comparative Examples 8 and 9, respectively, except that3-aminopropyltriethoxysilane (ATS) was used as a silane coupling agentinstead of octadecyltriethoxysilane (OTS). The obtained composites wereevaluated in the same manner as in Reference Example 1. The preparationconditions and evaluation results of these composite material are shownin Table R10 below.

TABLE 3 Table R1 Thermally modified polymer layer Preparation conditionMaterial First thermally Second thermally Third thermally Result Polymermodified modified modified of concen- polymer layer polymer layerpolymer layer Polymer member cross Inorganic tration Temp. Time Temp.Time Temp. Time Bonding cut substrate Solvent Polymer (mass %) (° C.)(min) (° C.) (min) (° C.) (min) Material method test Ref. Ex. 1 SiChloroform COP1*¹ 7 280 1 200 2 COP1 Spin A coating Ref. Ex. 2 SiChloroform COP1 3 280 1 200 2 COP1 Spin A coating Ref. Ex. 3 SiChloroform COP1 1 280 1 200 2 COP1 Spin A coating Ref. Ex. 3A SiChloroform COP1 1 300 1 280 1 200 2 COP1 Spin A coating Ref. Ex. 4*² SiChloroform COP1 1 280 1 200 2 COP1 Spin A coating Ref. Comp. Si COP1Spin C Ex. 1 coating *¹COP1 is a cyclic olefin polymer(JSR Corporation,ARTON ™) *²Reference Ex. 4 iSidentical to Reference Ex. 3 except thatthe rotation speed of the spin coating in preparation of thermallymodified polymer layer was changed from 2000 rpm to 6000 rpm

TABLE 4 Table R2 Thermally modified polymer layer Preparation conditionMaterial First thermally Second thermally Result Polymer modifiedmodified of concen- polymer layer polymer layer Polymer member crossInorganic tration Temp. Time Temp. Time Bonding cut substrate SolventPolymer (mass %) (° C.) (min) (° C.) (min) Material method test Ref. Ex.5 Si Chloroform COP1*¹ 7 360 1 200 2 COP1 Spin B coating Ref. Ex. 6 SiChloroform COP1 7 320 1 200 2 COP1 Spin B coating Ref. Ex. 1 SiChloroform COP1 7 280 1 200 2 COP1 Spin A coating Ref. Ex. 7 SiChloroform COP1 7 240 1 200 2 COP1 Spin B coating Ref. Ex. 8 SiChloroform COP1 7 200 1 200 2 COP1 Spin B coating Ref. Comp. Si COP1Spin C Ex. 1 coating *¹COP1 is a cyclic olefin polymer(JSR Corporation,AHTON ™)

TABLE 5 Table R3 Thermally modified polymer layer Preparation conditionMaterial First thermally Second thermally Result Polymer modifiedmodified of concen- polymer layer polymer layer Polymer member crossInorganic tration Temp. Time Temp. Time Bonding cut substrate SolventPolymer (mass %) (° C.) (min) (° C.) (min) Material method test Ref. Ex.9 Si Chloroform COP1*¹ 7 280 1 200 2 COP1 (※) A film Ref. Comp. Si COP1(※) C Ex. 2 film *¹COP1 is a cyclic olefin polymer (JSR Corporation,ARTON ™) (※) Thermocompression bonding

TABLE 6 Table R4 Thermally modified polymer layer Preparation conditionMaterial First thermally Second thermally Result Polymer modifiedmodified of concen- polymer layer polymer layer Polymer member crossInorganic tration Temp. Time Temp. Time Bonding cut substrate SolventPolymer (mass %) (° C.) (min) (° C.) (min) Material method test Ref. Ex.10 Si Chloroform COP1*¹ 7 360 1 COP1 Spin B coating Ref. Ex. 11 SiChloroform COP1 7 320 1 COP1 Spin B coating Ref. Ex. 12 Si ChloroformCOP1 7 280 1 COP1 Spin B coating Ref. Ex. 13 Si Chloroform COP1 7 240 1COP1 Spin B coating Ref. Ex. 14 Si Chloroform COP1 7 200 1 COP1 Spin Bcoating Ref. Comp. Si COP1 Spin C Ex. 1 coating *¹COP1 is a cyclicolefin polymer (JSR Corporation, ARTON ™)

TABLE 7 Table R5 Thermally modified polymer layer Preparation conditionMaterial First thermally Second thermally Result Polymer modifiedmodified of concen- polymer layer polymer layer Polymer member crossInorganic tration Temp. Time Temp. Time Bonding cut substrate SolventPolymer (mass %) (° C.) (min) (° C.) (min) Material method test Ref. Ex.15 Si Toluene COP2*³ 10 280 1 200 2 COP2 Spin A coating Ref. Ex. 16 SiToluene COP2 1 280 1 200 2 COP2 Spin A coating Ref. Comp. Si COP2 Spin CEx. 3 coating *³COP2 is a cyclic olefin polymer (Zeon Corporation,Zeonex ™ 480R)

TABLE 8 Table R6 Thermally modified polymer layer Preparation conditionMaterial First thermally Second thermally Result Polymer modifiedmodified of concen- polymer layer polymer layer Polymer member crossInorganic tration Temp. Time Temp. Time Bonding cut substrate SolventPolymer (mass %) (° C.) (min) (° C.) (min) Material method test Ref. Ex.17 Si Toluene COP2*³ 10 360 1 200 2 COP2 Spin B coating Ref. Ex. 18 SiToluene COP2 10 320 1 200 2 COP2 Spin B coating Ref. Ex. 10 Si TolueneCOP2 10 280 1 200 2 COP2 Spin A coating Ref. Ex. 19 Si Toluene COP2 10240 1 200 2 COP2 Spin B coating Ref. Ex. 20 Si Toluene COP2 10 200 1 2002 COP2 Spin B coating Ref. Comp. Si COP2 Spin C Ex. 3 coating *³COP2 isa cyclic olefin polymer (Zeon Corporation, Zeonex ™ 480R)

TABLE 9 Table R7 Thermally modified polymer layer Preparation conditionFirst thermally Second thermally Result modified modified of polymerlayer polymer layer Polymer member cross Inorganic Temp. Time Temp. TimeBonding cut substrate Material (° C.) (min) (° C.) (min) Material methodtest Ref. Ex. 21 Si PE film*⁴ 280 1 200 2 PE film (※) A Ref. Comp. Si PEfilm (※) C Ex. 4 *⁴PE film is a polyethylene film (thickness of 30 μm)(※) Thermocompression bonding

TABLE 10 Table R8 Thermally modified polymer layer Preparation conditionMaterial First thermally Second thermally Result Polymer modifiedmodified of concen- polymer layer polymer layer Polymer member crossInorganic tration Temp. Time Temp. Time Bonding cut substrate SolventPolymer (mass %) (° C.) (min) (° C.) (min) Material method test Ref. Ex.22 Si Chloroform COP1*¹ 7 280 1 200 2 COP2 Spin B coating Ref. Ex. 23 SiChloroform COP1 7 280 1 200 2 PE film (※) B Ref. Ex. 24 Si TolueneCOP2*³ 10 280 1 200 2 COP1 Spin A coating Ref. Ex. 25 Si Toluene COP2 10280 1 200 2 PE film (※) B Ref. Ex. 26 Si PE film*⁴ 280 1 200 2 COP1 SpinB coating Ref. Ex. 27 Si PE film 280 1 200 2 COP2 Spin B coating Ref.Comp. Si COP1 Spin C Ex. 1 coating Ref. Comp. Si COP2 Spin C Ex. 3coating Ref. Comp. Si PE film (※) C Ex. 4 *¹COP1 is a cyclic olefinpolymer (JSR Corporation, ARTON ™) *³COP2 is a cyclic olefin polymer(Zeon Corporation, Zeonex ™ 480R) *⁴PE film is a polyethylene film(thickness of 30 μm) (※) Thermocompression bonding

TABLE 11 Table R9 Thermally modified polymer layer Preparation conditionMaterial First thermally Second thermally Result Polymer modifiedmodified of concen- polymer layer polymer layer Polymer member crossInorganic tration Temp. Time Temp. Time Bonding cut substrate SolventPolymer (mass %) (° C.) (min) (° C.) (min) Material method test Ref. Ex.28 SiN Toluene COP2*³ 10 280 1 200 2 COP2 Spin A coating Ref. Comp. SiNCOP2 Spin C Ex. 5 coating Ref. Ex. 29 Cu Toluene COP2 10 280 1 200 2COP2 Spin A coating Ref. Comp. Cu COP2 Spin C Ex. 6 coating Ref. Ex. 30Al Toluene COP2 10 280 1 200 2 COP2 Spin A coating Ref. Comp. Al COP2Spin C Ex. 7 coating *³COP2 is a cyclic olefin polymer (ZeonCorporation, Zeonex ™ 480R )

TABLE 12 Table R10 Thermally modified polymer layer Preparationcondition Material First thermally Second thermally Result Polymermodified modified of concen- polymer layer polymer layer Polymer membercross Inorganic tration Temp. Time Temp. Time Bonding cut substrateSolvent Polymer (mass %) (° C.) (min) (° C.) (min) Material method testRef. Comp. OTS treated COP2*³ Spin C Ex. 8 Si coating Ref. Comp. OTStreated PE film*⁴ (※) C Ex. 9 Si Ref. Comp. PTS treated COP2 Spin C Ex.10 Si coating Ref. Comp. PTS treated PE film (※) C Ex. 11 Si Ref. Comp.ATS treated COP2 Spin C Ex. 12 Si coating Ref. Comp. ATS treated PE film(※) C Ex. 13 Si *³COP2 is a cyclic olefin polymer (Zeon Corporation,Zeonex ™ 480R) *⁴PE film is a polyethylene film (thickness of 30 μm) (※)Thermocompression bonding

<Evaluation Result>

From Table R1 above, it is understood that, when the polymerconcentration in the polymer solution for forming thermally modifiedpolymer layer was 1 to 7% by mass and the rotation speed of thespin-coating at the time of forming thermally modified polymer layer was2000 to 4000 rpm (Reference Examples 1 to 4), peeling of the polymermember was suppressed as compared with the case where the thermallymodified polymer layer was not used (Reference Comparative Example 1).

In addition, from Table R1 above, it is understood that, not only whentwo thermally modified polymer layers were used (Reference Examples 1 to4) but also when three thermally modified polymer layers were used(Reference Example 3A), peeling of the polymer member was suppressed ascompared with the case where the thermally modified polymer layer wasnot used (Reference Comparative Example 1).

From Table R2 above, it is understood that, when the thermalmodification temperature for forming thermally modified polymer layerwas 200° C. to 360° C. (Reference Examples 1 and 5 to 8), peeling of thepolymer member was suppressed as compared with a case where thethermally modified polymer layer was not used (Reference ComparativeExample 1).

From Table R3 above, it is understood that, when the polymer member filmwas bonded to the thermally modified polymer layer bythermocompression-bonding (Reference Example 9), peeling of the polymermember was suppressed as compared with the case where the polymer memberwas directly bonded to the silicon substrate bythermocompression-bonding without using the thermally modified polymerlayer (Reference Comparative Example 2).

From Table R4 above, it is understood that, even when only one thermallymodified polymer layer was used instead of two thermally modifiedpolymer layers (Reference Examples 10 to 14), peeling of the polymermember was suppressed as compared with the case where the thermallymodified polymer layer was not used (Reference Comparative Example 1)

From Table R5 above, it is understood that, when the polymerconcentration in the polymer solution for forming thermally modifiedpolymer layer was 1 to 10% by mass (Reference Examples 15 to 16),peeling of the polymer member was suppressed as compared with the casewhere the thermally modified polymer layer was not used (ReferenceComparative Example 3)

From Table R6 above, it is understood that, when the thermalmodification temperature for forming thermally modified polymer layerwas 200° C. to 360° C. (Reference Examples 10 and 17 to 20), peeling ofthe polymer member was suppressed as compared with the case where thethermally modified polymer layer was not used (Reference ComparativeExample 3).

From Table R7 above, it is understood that, when the polymer member filmwas bonded to the thermally modified polymer layer bythermocompression-bonding (Reference Example 21), peeling of the polymermember was suppressed as compared with the case where the polymer memberfilm was directly bonded to the silicon substrate bythermocompression-bonding without using the thermally modified polymerlayer (Reference Comparative Example 4).

From Table R8 above, it is understood that, even under the conditionwhere the polymer for forming thermally modified polymer layer and thepolymer for forming polymer member are different from each other, whenthe thermally modified polymer layer was used (Reference Examples 22 to27), peeling of the polymer member was suppressed, as compared with thecase where the thermally modified polymer layer was not used (ReferenceComparative Examples 1, 3 and 4).

From Table R9 above, it is understood that, even under the conditionwhere a silicon substrate with SiN formed on the surface thereof, acopper plate, and an aluminum plate were used as a substrate instead ofa silicon substrate, when the thermally modified polymer layer was used(Reference Examples 28 to 30), peeling of the polymer member wassuppressed, as compared with the case where the thermally modifiedpolymer layer was not used (Reference Comparative Examples 5 to 7).

From Table R10 above, it is understood that, even under the conditionwhere the substrate was a silicon substrate treated with a silanecoupling agent, peeling of the polymer member was not suppressed ascompared with the case where the thermally modified polymer layers wereused (Reference Examples).

Reference Examples 31 to 36

A silicon substrate was used as an inorganic substrate, and a siliconsubstrate with thermally modified polymer layer was obtained on thesilicon substrate in the same manner as in Reference Example 1, exceptthat a solution for thermally modified polymer layer was obtained bymixing and stirring 20% by mass of COP1 and 80% by mass of chloroform atroom temperature, and the temperature of the hot plate for thermalmodification was changed to 400° C. (Reference Example 31), 320° C.(Reference Example 32), 280° C. (Reference Example 33), 240° C.(Reference Example 34), 200° C. (Reference Example 35), and 160° C.(Reference Example 36).

(Elemental Analysis by XPS)

For the thermally modified polymer layers of Reference Examples 31 to36, a ratio of the number of oxygen atoms contained in the thermallymodified polymer layer to the total number of oxygen atoms and carbonatoms contained in the thermally modified polymer layer (number of Oatoms/(number of O atoms+number of C atoms) (%)) was determined using anXPS device (K-Alpha (from Thermo Fisher Scientific)).

Measurement was performed using monochromatized AlKα rays as an X-raysource and with a photoelectron extraction angle of 0 degree. The O1speak area was determined by drawing a baseline according to Shirleymethod in the range of 527 to 537 eV, and the C1s peak area wasdetermined by drawing a baseline according to Shirley method in therange of 280 to 290 eV. The oxygen concentration and carbonconcentration on the surface of the film were obtained by correcting theabove-mentioned O1s peak area and C1s peak area with a sensitivitycoefficient inherent to respective devices.

Preparation conditions and evaluation results of the thermally modifiedpolymer layer are shown in Table R11 below. It is understood from thisTable R11 that as the temperature for the thermal modificationdecreases, i.e. as the degree of thermal modification decreases, thisratio (number of O atoms/(number of O atoms+number of C atoms) (%))decreases. Therefore, it is understood that this ratio can be used as anindex of the degree of thermal modification of a thermally modifiedpolymer layer.

(Measurement of Infrared Absorption Spectrum)

For the thermally modified polymer layers of Reference Examples 31 to36, infrared transmission absorption spectrum ranging from 4000 to 500cm⁻¹ was measured using an IR absorption spectrometer (Nicolet 6700(from Thermo Fisher Scientific)) to determine the ratio of theabsorption peak intensity of C═O stretching vibration peaking at 1732cm⁻¹ to the absorption peak intensity of C—H stretching vibrationpeaking at 2947 cm⁻¹ (ratio of the absorption peak intensity of C═Ostretching vibration/the absorption peak intensity of C—H stretchingvibration (−)). The absorption peak intensity was determined by readingthe maximum value of the absorbance value of the absorption peak.

Preparation conditions and evaluation results of the thermally modifiedpolymer layer are shown in Table R11 below. It is understood from theTable R11 that as the temperature for thermal modification decreases,i.e. as the degree of thermal modification decreases, this ratio (aratio of absorption peak intensity of C═O stretchingvibration/absorption peak intensity of C—H stretching vibration (−))decreases. Therefore, it is understood that this ratio can be used as anindex of the degree of thermal modification of a thermally modifiedpolymer layer.

TABLE 13 Table R11 Thermally modified polymer layer Material Number of Oatoms/ Ratio of Polymer Preparation condition (Number of O atoms +absorption Inorganic concentration Temp. Time Number of C atoms)intensity substrate Solvent Polymer (mass %) (° C.) (min) (%) (—) Ref.Ex. 31 Si Chloroform COP1 20 400 1 (not measured) 3.10 Ref. Ex. 32 SiChloroform COP1 20 320 1 7.1 0.25 Ref. Ex. 33 Si Chloroform COP1 20 2801 6.3 0.22 Ref. Ex. 34 Si Chloroform COP1 20 240 1 0.1 0 Ref. Ex. 35 SiChloroform COP1 20 200 1 0.1 0 Ref. Ex. 36 Si Chloroform COP1 20 160 1(not measured) 0

REFERENCE SIGNS

-   10 inorganic substrate-   20, 21, 22 thermally modified polymer layer-   30, 31, 32 polymer member-   110, 120 composite of thermally modified polymer layer and inorganic    substrate-   210, 220 composite of polymer member and inorganic substrate    according to the present invention

1. A method for manufacturing a composite of polymer member andinorganic substrate, comprising: providing a composite of thermallymodified polymer layer and inorganic substrate in which one or morethermally modified polymer layers are adhered onto an inorganicsubstrate, and bonding a polymer member to the inorganic substrate viathe one or more thermally modified polymer layers, wherein the polymermember at least comprises inorganic particles and a polymer.
 2. Themethod according to claim 1, wherein the polymer member furthercomprises a coupling agent.
 3. The method according to claim 1, whereinthe polymer member is in the form of a membrane or film.
 4. The methodaccording to claim 1, wherein the bonding of the polymer member isperformed by thermocompression bonding.
 5. The method according to claim1, wherein the one or more thermally modified polymer layers are formedof an olefin polymer, and the polymer of the polymer member is an olefinpolymer.
 6. The method according to claim 5, wherein the olefin polymeris a cyclic olefin polymer.
 7. The method according to claim 1, whereinthe inorganic substrate is selected from a group consisting of metalsand metalloids, metal oxides and metalloid oxides, metal nitrides andmetalloid nitrides, metal carbides and metalloid carbides, carbonmaterials, and combinations thereof.
 8. A composite of polymer memberand inorganic substrate, comprising: an inorganic substrate, one or morethermally modified polymer layers adhered to the inorganic substrate,and a polymer member adhered to the inorganic substrate via the one ormore thermally modified polymer layers, wherein the polymer member atleast comprises inorganic particles and a polymer.
 9. The compositeaccording to claim 8, wherein the polymer member further comprises acoupling agent.
 10. The composite according to claim 8, wherein thepolymer member is in the form of a membrane or film.
 11. The compositeaccording to claim 8, wherein the one or more thermally modified polymerlayers are formed of an olefin polymer, and the polymer of the polymermember is an olefin polymer.
 12. The composite according to claim 11,wherein the olefin polymer is a cyclic olefin polymer. 13-21. (canceled)